This invention relates to electrochromic devices and, more particularly, to electrochromic light filters or windows, as well as electrochromic and rearview mirrors having an improved seal member.
Heretofore, devices of reversibly variable transmittance to electromagnetic radiation have been proposed as the variable transmittance element in variable transmittance lightfilters, variable reflectance mirrors, and display devices which employ such lightfilters or mirrors in conveying information. These variable transmittance light filters have included windows. One commercially available device is an electrochromic mirror for motor vehicles. These electrochromic mirrors change from the full reflectance mode (day) to the partial reflectance mode(s) (night) for glare-protection purposes from light emanating from the headlights of vehicles approaching from the rear. Among such devices are those wherein the transmittance is varied by thermochromic, photochromic, or electro-optic (e.g., liquid crystal, dipolar suspension, electrophoretic, electrochromic, etc.) means and where the variable transmittance characteristic affects electromagnetic radiation that is at least partly in the visible spectrum (wavelengths from about 3800 .ANG. to about 7800 .ANG.).
Devices of reversibly variable transmittance to electromagnetic radiation, wherein the transmittance is altered by electrochromic means, are described, for example, by Chang, "Electrochromic and Electrochemichromic Materials and Phenomena, " in Non-emissive Electrooptic Displays, A. Kmetz and K. von Willisen, eds. Plenum Press, New York, N.Y. 1976, pp. 155-196 (1976) and in various parts of Eletrochromism, P. M. S. Monk, R. J. Mortimer, D. R. Rosseinsky, VCH Publishers, Inc., New York, N.Y. (1995). Numerous electrochromic devices are known in the art. See, e.g., Manos, U.S. Pat. No. 3, 451, 741; Bredfeidt et al., U.S. Pat. No. 4, 090, 358;Clecak et al., U.S. Pat. No. 4, 139, 276; Kissa et al., U.S. Pat. No. 3, 453, 038;Rogers, U.S. Pat. Nos. 3, 652, 149, 3, 774, 988 and 3, 873, 185; and Jones et al., U.S. Pat. Nos. 3, 282, 157, 3, 282, 158, 3, 282, 160 and 3, 283, 656.
In addition to these devices there are commercially available electrochromic devices and associated circuitry, such as those disclosed in U.S. Pat. No. 4, 902, 108, entitled "Single-Compartment, Self-Erasing, Solution-Phase Electrochromic Devices Solutions for Use Therein, and Uses Thereof", issued Feb. 20, 1990 to H. J. Byker; Canadian Patent No. 1,300,945, entitled "Automatic Rearview Mirror System for Automotive Vehicles", issued May 19, 1992 to J. H. Bechtel et al.; U.S. Pat. No. 5,128,799, entitled "Variable Reflectance Motor Vehicle Mirror", issued Jul. 7, 1992 to H. J. Byker; U.S. Pat. No. 5, 202, 787, entitled "Electro-Optic Device", issued Apr. 13, 1993 to H. J. Byker et al.; U.S. Patent No. 5,204,778, entitled "Control System For Automatic Rearview Mirrors", issued Apr. 20, 1993 to J. H. Bechtel; U.S. Patent No. 5,278,693, entitled "Tinted Solution-Phase Electrochromic Mirrors", issued Jan. 11, 1994 to D. A. Theiste et al.; U.S. Pat. No. 5,280,380, entitled "UV-Stabilized Compositions and Methods", issued Jan. 18, 1994 to H. J. Byker; U.S. Pat. No. 5,282,077, entitled "Variable Reflectance Mirror", issued Jan. 25, 1994 to H. J. Byker; U.S. Pat. No. 5,294,376, entitled "Bipyridinium Salt Solutions", issued Mar. 15, 1994 to H. J. Byker; U.S. Pat. No. 5,336,448, entitled "Electrochromic Devices with Bipyridinium Salt Solutions", issued Aug. 9, 1994 to H. J. Byker; U.S. Pat. No. 5,434,407, entitled "Automatic Rearview Mirror Incorporating Light Pipe", issued Jan. 18, 1995 to F. T. Bauer et al.; U.S. Pat. No. 5,448,397, entitled "Outside Automatic Rearview Mirror for Automotive Vehicles", issued Sep. 5, 1995 to W. L. Tonar; and U.S. Pat. No. 5,451,822, entitled "Electronic Control System", issued Sep. 19, 1995 to J. H. Bechtel et al. Each of these patents is commonly assigned with the present invention and the disclosures of each, including the references contained therein, are hereby incorporated herein in their entirety by reference. Such electrochromic devices may be utilized in a fully integrated inside/outside rearview mirror system or as separate inside or outside rearview mirror systems.
FIG. 1 shows a typical electrochronic mirror device 10, having front and rear planar elements 12 and 16, respectively. A transparent conductive coating 14 is placed on the rear face of the front element 12, and another transparent conductive coating 18 is placed on the front face of rear element 16. A reflector (20a, 20b and 20c), typically comprising a silver metal layer 20a, covered by a protective copper metal layer 20b, and one or more layers of protective paint 20c, is disposed on the rear face of the rear element 16. For clarity of description of such a structure, the front surface of the front glass element is sometimes referred to as the first surface, and the inside surface of the front glass element is sometimes referred to as the second surface. The inside surface of the rear glass element is sometimes referred to as the third surface, and the back surface of the rear glass element is sometimes referred to as the fourth surface. The front and rear elements are held in a parallel and spaced-apart relationship by seal 22, thereby creating a chamber 26. The electrochromic medium 24 is contained in space 26. The electrochromic medium 24 is in electrical contact with transparent electrode layers 14 and 18, through which passes electromagnetic radiation whose intensity is reversibly modulated in the device by a variable voltage or potential applied to electrode layers 14 and 18 through clip contacts and an electronic circuit (not shown).
Typically seal 22 is made from an organic material and is used to bond two inorganic glass elements together. This may cause problems ensuring adequate seal integrity over long periods of time because of the difference in the coefficient of thermal expansion (CTE) between the seal and the glass transparent elements. In addition, it is known to place a small percentage of glass beads, e.g., 1/2 to 2 percent by weight, into the seal as spacers to ensure uniform spacing of the glass transparent elements. This CTE mismatch problem is pronounced (with or without spacer beads) for electrochromic devices that are operated over a wide temperature range, such as architectural windows and automotive windows. Architectural windows must have adequate seal integrity during summer and winter where the temperature may vary by more than 130.degree. F.
Even before a fourth surface reflector electrochromic mirror was commercially available, various groups researching electrochromic devices had discussed moving the reflector from the fourth surface to the third surface. Such a mirror design has advantages in that it should, theoretically, be easier to manufacture because there are fewer layers to build into a device, i.e., the third surface transparent electrode is not necessary when there is a third surface reflector/electrode. In addition, electrochromic windows have been proposed with a very thin layer of metal for use as an electrode on the second surface or third surface or both surfaces. The advantage of using a thin metal layer for use in a light filter or window is that a lower sheet resistance of the electrode can be obtained. In practice, however, placing the thin metal layer on the second or third surface, or the reflector on the third surface, has been difficult. One reason for this difficulty is that the seal used to bond the two pieces of glass together and hold them in a spaced-apart relationship does not always bond well with certain metals, especially reflective and noble metals.
Consequently, it is desirable to provide an improved electrochromic device having a seal that bonds well to a conductive electrode comprising a metal. In addition, it is desirable to provide an electrochromic device having a seal that has a coefficient of thermal expansion that more closely matches the transparent elements.